CN105073722B - The manufacture method of (methyl) glycidyl acrylate - Google Patents

Abstract

The present invention provides glycidyl (meth)acrylate having a low content of chlorine-containing impurities. The present invention provides a kind of manufacture method of (meth) glycidyl acrylate, is to make epichlorohydrin and (meth)acrylic acid alkali metal salt react in the presence of catalyst to manufacture the method for (meth) glycidyl acrylate, This includes the step of performing the above-mentioned reaction while presenting 0.0001 mol to 0.08 mol of Bronsted acid with respect to 1 mol of the (meth)acrylic acid alkali metal salt in the reaction system.

Description

The production method of glycidyl (meth)acrylate

technical field

The present invention relates to a method for producing glycidyl (meth)acrylate.

Background technique

As a typical synthetic method of glycidyl (meth)acrylate, the method using epichlorohydrin as a raw material is mentioned. This method is roughly classified into the following two methods.

The first method is a method of synthesizing glycidyl (meth)acrylate by reacting epichlorohydrin and an alkali metal (meth)acrylate in the presence of a catalyst (Patent Document 1). The second method is a method of synthesizing glycidyl (meth)acrylate by reacting epichlorohydrin and (meth)acrylic acid in the presence of a catalyst, followed by a ring-closing reaction with an alkaline aqueous solution (Patent Document 2). The method described in Patent Document 1 has a higher yield than the method described in Patent Document 2.

prior art literature

patent documents

Patent Document 1: Japanese Patent Application Laid-Open No. 7-2818

Patent Document 2: Japanese Patent Application Laid-Open No. 7-118251

Contents of the invention

However, the raw material epichlorohydrin has a reactive epoxy group, so a large number of side reactions occur. In particular, chlorine-containing impurities, which are difficult to separate by distillation, are by-produced, and their suppression is a problem. Therefore, in the synthesis method of glycidyl (meth)acrylate, it is desired to reduce many known by-products by a simple and low-cost method.

An object of the present invention is to provide glycidyl (meth)acrylate having a low content of chlorine-containing impurities.

The present invention relates to the following [1] to [5].

[1] A method for producing glycidyl (meth)acrylate, comprising reacting epichlorohydrin and an alkali metal (meth)acrylate in the presence of a catalyst to produce glycidyl (meth)acrylate, It includes:

In the reaction system, the step of carrying out the above-mentioned reaction is carried out in the presence of 0.0001 mol to 0.08 mol of Bronsted acid with respect to 1 mol of the alkali metal (meth)acrylate.

[2] The method for producing glycidyl (meth)acrylate according to [1], wherein the Bronsted acid is at least one of carboxylic acid and sulfonic acid.

[3] The method for producing glycidyl (meth)acrylate according to [2], wherein the Bronsted acid is at least one selected from (meth)acrylic acid, benzoic acid, acetic acid, and methanesulfonic acid. kind.

[4] The method for producing glycidyl (meth)acrylate according to any one of [1] to [3], comprising: washing the reaction liquid obtained by the above reaction with water, and statically washing the washed liquid A step of disposing and separating the organic cleaning layer, and a step of distilling the liquid of the organic cleaning layer.

[5] Glycidyl (meth)acrylate containing 500 ppm or less of impurities in terms of total chlorine.

According to the present invention, glycidyl (meth)acrylate having a low content of chlorine-containing impurities can be provided.

detailed description

The method involved in the present invention is to make epichlorohydrin and (meth)acrylic acid alkali metal salt react in the presence of a catalyst to produce glycidyl (meth)acrylate, which includes: in the reaction system, relative to ( The step of carrying out the above reaction in the presence of 0.0001 mol to 0.08 mol of Bronsted acid per mol of alkali metal meth)acrylate. In the present invention, in the reaction between epichlorohydrin and alkali metal (meth)acrylate, by making the Bronsted acid exist in the amount within the above range, chlorine-containing chloropropenyl (meth)acrylate and the like can be suppressed. By-products of impurities. Thereby, glycidyl (meth)acrylate containing a small content of the chlorine-containing impurity which is difficult to isolate|separate by distillation can be obtained. In addition, the method involved in the present invention may further include, in addition to the reaction step of performing the above reaction, the step of washing the reaction liquid obtained by the above reaction with water, leaving the washed liquid to stand and separating the organic cleaning layer; and A distillation step of liquid distillation of the above-mentioned organic cleaning layer. The details of each step of the method according to the present invention are shown below.

[Reaction Process]

The method according to the present invention includes a step of reacting epichlorohydrin and an alkali metal (meth)acrylate in the presence of a catalyst. In the present invention, glycidyl (meth)acrylate is produced by the reaction of epichlorohydrin and alkali metal (meth)acrylate. In this reaction, in this invention, 0.0001-0.08 mol of Bronsted acid exists with respect to 1 mol of alkali metal (meth)acrylate salts. The Bronsted acid is preferably at least one of carboxylic acid and sulfonic acid from the viewpoint of solubility in the reaction liquid and ease of handling. Furthermore, the Bronsted acid is more preferably at least one selected from (meth)acrylic acid, benzoic acid, acetic acid, and methanesulfonic acid from the viewpoint of availability and price. In addition, (meth)acrylic acid means methacrylic acid or acrylic acid, and (meth)acrylic acid alkali metal salt means methacrylic acid alkali metal salt or acrylate alkali metal salt.

Although it does not specifically limit as an alkali metal (meth)acrylate, For example, sodium (meth)acrylate, potassium (meth)acrylate, lithium (meth)acrylate, etc. can be used. These may be used alone or in combination of two or more.

Alkali metal (meth)acrylates can be prepared by neutralization of (meth)acrylic acid with alkali metal hydroxides. Although it does not specifically limit as an alkali metal hydroxide, Sodium hydroxide, potassium hydroxide, lithium hydroxide etc. are preferable. These may be used alone or in combination of two or more.

The mixing ratio of (meth)acrylic acid and alkali metal hydroxide is preferably 0.9 to 1.1 moles of alkali metal hydroxide, more preferably 0.95 to 1.05 moles, and still more preferably 0.99 to 1 mole of (meth)acrylic acid. 1.01 mol. The closer the obtained reaction liquid is to neutrality, the more the side reaction at the time of synthesizing glycidyl (meth)acrylate can be suppressed. At this time, if (meth)acrylic acid is slightly mixed with the alkali metal hydroxide, in the reaction with epichlorohydrin, (meth)acrylic acid can be present within the range of the amount of the present invention as Bronsted acids are therefore preferred. Moreover, since the smell of (meth)acrylic acid can be suppressed when the alkali metal hydroxide is mixed slightly more than (meth)acrylic acid, it is industrially preferable. However, the remaining alkali components sometimes induce side reactions in the reaction with epichlorohydrin. For this problem, the method of making a Bronsted acid exist according to the present invention is effective. It should be noted that when the prepared (meth)acrylic acid alkali metal salt contains an alkali metal hydroxide, it is considered that the Bronsted acid is neutralized by the alkali metal hydroxide, so as to be relative to the (meth)acrylic acid alkali metal salt 1 The Bronsted acid is added so that 0.0001 to 0.08 moles of the Bronsted acid is present. Since the amount of alkali metal hydroxide to be neutralized can be calculated from the amount of each raw material added, the amount of Bronsted acid required for neutralization of the alkali metal hydroxide can also be calculated.

A solvent can also be used when neutralizing (meth)acrylic acid with an alkali metal hydroxide. As the solvent, alcohols such as methanol and water are preferably used from the viewpoint of solubility. When a solvent is used, the solvent may be removed after neutralization. As a solvent removal method, a known method can be used, for example, distillation, spray drying, etc. can be used.

The temperature of the reaction liquid during neutralization is preferably -10°C to 80°C from the viewpoint of polymerization suppression and cooling efficiency. In order to suppress polymerization, a polymerization inhibitor may also be added.

In the present invention, when epichlorohydrin and an alkali metal (meth)acrylate are reacted in the presence of a catalyst, 0.0001 to 0.08 mol of Bronsted acid is present with respect to 1 mol of the alkali metal (meth)acrylate. The side reaction can be fully suppressed by making Brønsted acid 0.0001 mol or more exist. In addition, by making Bronsted acid 0.08 mol or less, low cost can be realized, and side reactions can be sufficiently suppressed. In the above step, the Bronsted acid is preferably present in an amount of 0.001 to 0.075 mol, more preferably 0.005 to 0.07 mol, and still more preferably 0.01 to 0.05 mol, based on 1 mol of the alkali metal (meth)acrylate. In addition, the amount of the Bronsted acid with respect to the alkali metal (meth)acrylic acid salt existing in a reaction system can be calculated from the addition amount of each raw material.

In particular, the presence of Bronsted acid within the above-mentioned range suppresses the generation of chlorine-containing impurities. Chlorine-containing impurities mainly include chloropropenyl (meth)acrylate represented by the following formula (1) and 1,3-dichloro-2-propanol.

R in the above formula (1) represents hydrogen or methyl. In particular, chloroallyl (meth)acrylate represented by the above formula (1) has a small boiling point difference with glycidyl (meth)acrylate, so it cannot be separated by distillation and is mixed into the product. The inventors of the present invention found that by adding a Bronsted acid to the presence of a Bronsted acid at the time of addition of raw materials, in particular, the amount of chloroallyl (meth)acrylate represented by the above formula (1) can be reduced. amount of by-products. It was confirmed that chloroallyl (meth)acrylate increases when a small amount of basic compound exists, and it is considered that Bronsted acid has an effect of neutralizing the basic compound present in a small amount.

The Bronsted acid existing in the reaction system can exist by excessive use of (meth)acrylic acid in the preparation of the alkali metal salt of (meth)acrylate, and can also be present in the reaction system before the reaction starts or at the early stage of the reaction. Add the Bronsted acid. In the present invention, the early stage of the reaction refers to the time from the time of mixing the raw material compounds to the time when heating is started, the predetermined reaction temperature is reached, and the conversion rate based on the alkali metal (meth)acrylate is 50 mol% or less.

The reaction between epichlorohydrin and alkali metal (meth)acrylate is carried out in the presence of a catalyst. As a catalyst, for example, a quaternary ammonium salt, an ion exchange resin having the quaternary ammonium salt, or the like can be used. As the quaternary ammonium salt, for example, tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, etc. can be used Tetraalkylammonium salts. As the ion exchange resin, a commercially available strongly basic anion exchange resin can be used. These may be used alone or in combination of two or more.

In the reaction of epichlorohydrin and an alkali metal salt of (meth)acrylate, and the neutralization reaction of (meth)acrylic acid and an alkali metal hydroxide, a polymerization inhibitor can be used in order to suppress polymerization. As the polymerization inhibitor, for example, phenols such as hydroquinone and p-methoxyphenol, amines such as phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N- Oxygen (HO-TEMPO) and other N-oxygen systems, etc. These may be used alone or in combination of two or more. In addition, in order to prevent polymerization, it is preferable to bubble oxygen or air during the reaction.

The reaction temperature in the reaction of epichlorohydrin and alkali metal (meth)acrylate can be appropriately selected according to the amount of the catalyst to be used, but is preferably 40°C to 150°C, more preferably 50°C to 140°C. A sufficient reaction rate can be obtained by making reaction temperature 40 degreeC or more. In addition, by making the reaction temperature 150° C. or lower, by-product formation can be suppressed.

The molar ratio of epichlorohydrin and alkali metal (meth)acrylate used in the reaction of epichlorohydrin and alkali metal (meth)acrylate is not particularly limited, preferably relative to the alkali metal (meth)acrylate 1 mol of epichlorohydrin is 1.0 to 20.0 mol, more preferably 1.5 to 10.0 mol. By making epichlorohydrin 1.0 mol or more, the conversion rate based on an alkali metal (meth)acrylate can be improved. In addition, the yield per reaction can be increased by setting the epichlorohydrin to be 20.0 mol or less.

The amount of the catalyst used for the reaction of epichlorohydrin and the alkali metal (meth)acrylate is preferably 0.01 to 10 mol, more preferably 0.05 to 5 mol, based on 1 mol of the alkali metal (meth)acrylate. A sufficient reaction rate can be acquired by making the quantity of a catalyst into 0.01 mol or more with respect to 1 mol of alkali metal (meth)acrylates. Moreover, by making the quantity of a catalyst into 10 mol or less with respect to 1 mol of alkali metal (meth)acrylic acid salts, formation of a by-product can be suppressed.

The amount of the polymerization inhibitor used for the reaction of epichlorohydrin and the alkali metal (meth)acrylate is preferably 10 to 10,000 mass ppm, more preferably 50 to 5,000 mass ppm relative to the mass of the alkali metal (meth)acrylate ppm. By making the quantity of a polymerization inhibitor into 10 mass ppm or more, superposition|polymerization can fully be suppressed. Moreover, by making the quantity of a polymerization inhibitor into 10000 mass ppm or less, generation|occurrence|production of the quality deterioration by coloring of a product etc. can be suppressed.

[washing process]

The method according to the present invention preferably includes the steps of washing a reaction liquid obtained by reacting epichlorohydrin and an alkali metal (meth)acrylate with water, leaving the washed liquid to stand, and separating the organic cleaning layer. In the reaction liquid after the reaction, besides glycidyl (meth)acrylate, alkali metal chlorides, catalysts, excess epichlorohydrin, by-products and the like are present. By washing the reaction liquid with washing water, the alkali metal chloride, catalyst, and specific by-products can be dissolved in the water layer and separated and removed.

As washing water used for water washing, water or an aqueous solution in which a basic compound is dissolved can be used. Although it does not specifically limit as a basic compound, For example, alkali metal hydroxide, alkali metal carbonate, alkali metal bicarbonate etc. are mentioned. Specifically, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, etc. are mentioned. These may be used alone or in combination of two or more. The amount of the basic compound contained in the washing water is preferably 0 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, and even more preferably 0.2 to 20 parts by mass relative to 100 parts by mass of water constituting the washing water. By setting the amount of the basic compound within the above range, the generation of by-products can be sufficiently suppressed.

The amount of washing water used in the water washing step is preferably an amount capable of sufficiently dissolving the alkali metal chloride, the catalyst, and the like. Specifically, the amount of washing water is preferably 160 to 2000 g, more preferably 180 to 1500 g, based on 1 mol of the alkali metal (meth)acrylate added during the reaction. By setting the amount of washing water to be 160 g or more, the alkali metal chloride, the catalyst, and the like can be sufficiently dissolved. Moreover, productivity improves by making the quantity of washing|cleaning water into 2000g or less.

When washing with water, it can be stirred by a known stirring method. For example, the reaction solution and washing water can be sufficiently stirred and mixed using a stirrer equipped with stirring blades. The stirring time is not particularly limited, and may be, for example, 3 to 60 minutes.

The reaction liquid can be separated into a washing organic layer and a water layer by stirring and mixing the reaction liquid with washing water and then standing still. The liquid in which the organic layer was washed can be purified by the following distillation process.

[distillation process]

The method according to the present invention may include the step of distilling the above liquid for washing the organic layer. High-purity glycidyl (meth)acrylate can be obtained by distilling the liquid in which the organic layer was washed. The distillation of the liquid for washing the organic layer can be performed by a known method. From the viewpoint of obtaining higher-purity glycidyl (meth)acrylate, it is preferable to perform rectification using a column. Distillation may be batch or continuous, and the batch precision distillation will be described below.

Since glycidyl (meth)acrylate is a polymerizable monomer, polymerization can be suppressed by distillation at a lower temperature under reduced pressure. From the above viewpoint, the temperature of the distillation pot is preferably 160°C or lower, more preferably 150°C or lower. On the other hand, from the viewpoint of distillation efficiency, the temperature of the distillation pot is preferably 60°C or higher, more preferably 70°C or higher. In addition, from the viewpoint of the decompression limit, the degree of decompression is preferably 0.1 kPa or more, more preferably 0.5 kPa or more. On the other hand, from the viewpoint of lowering the temperature, the degree of reduced pressure is preferably 50 kPa or less, more preferably 30 kPa or less.

In order to suppress polymerization, a known polymerization inhibitor can be supplied to the inside of the distillation pot and the inside of the column. As a polymerization inhibitor, for example, phenols such as hydroquinone and p-methoxyphenol, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (HO-TEMPO), etc. can be used. N-oxygen system, etc. These may be used alone or in combination of two or more. In addition, in order to prevent polymerization, it is preferable to bubble oxygen or air during distillation.

For the rectification operation using a column, known methods can be used. As the tower, a known device such as a packed tower using a laminate or a packing material can be used. Purity can be improved by controlling the reflux ratio during distillation. Specifically, the reflux ratio is preferably in the range of 0.1 to 10, more preferably in the range of 0.3 to 3, from the viewpoint of ensuring purity and productivity.

According to the method according to the present invention, glycidyl (meth)acrylate containing impurities of 500 ppm or less in terms of the total amount of chlorine can be obtained. That is, according to the method according to the present invention, glycidyl (meth)acrylate containing chlorine (Cl)-containing compounds (impurities) of 500 ppm or less in total chlorine (Cl) can be obtained. Here, the impurities include chlorine-containing impurities and chlorine-free impurities. However, among chlorine-containing impurities, there are impurities that are difficult to remove even by distillation, and these eventually remain as impurities. Therefore, in the present invention, the content of impurities is represented by the total amount of chlorine contained in glycidyl (meth)acrylate. In addition, in the distillate after distillation, chlorine other than chlorine contained in impurities hardly exists. The glycidyl (meth)acrylate may contain impurities of 450 ppm or less in terms of total chlorine, may contain impurities of 400 ppm or less in total chlorine, or may contain impurities of 300 ppm or less in total chlorine. It should be noted that the amount of impurities is preferably as small as possible in terms of the total amount of chlorine contained in glycidyl (meth)acrylate, and may be 0 ppm. In addition, the total chlorine content was determined by heating the distillation distillate to 100-900°C using a sample combustion device QF-02 (trade name, manufactured by Mitsubishi Chemical Corporation), and burning the gas after absorbing the gas in the absorber tube, and measuring it as IC (ion Chromatography) to analyze and quantify the value.

Example

Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to them. The analysis of each compound in Examples and Comparative Examples used gas chromatography (GC).

[Total Chlorine Determination Method]

Using a sample combustion device QF-02 (trade name, manufactured by Mitsubishi Chemical Corporation), the distillation distillate is heated to 100 to 900°C and burned, and the gas is absorbed in the absorption tube, and then analyzed by IC (ion chromatography). Measure total chlorine.

(Example 1)

0.04 g of benzoyl esters of HO-TEMPO as a polymerization inhibitor were dissolved in 387.4 g (4.5 mol) of methacrylic acid. This solution was mixed with an aqueous solution obtained by dissolving 180 g (4.5 mol) of sodium hydroxide in 420 g of water. The mixed solution was spray-dried with hot air. Thus, sodium methacrylate was obtained. It should be noted that methacrylic acid was not detected in this sodium methacrylate.

Prepare a 50 ml flask equipped with a thermometer, an air introduction tube, a stirring wing, and a cooling tube. In this flask, add 4.435 g (0.041 mol) of the above-mentioned sodium methacrylate, 0.0185 g (0.00017 mol) of tetramethylammonium chloride as a catalyst, 0.0005 g of benzoyl ester body of HO-TEMPO as a polymerization inhibitor, 19.8 g (0.214 mol) of epichlorohydrin, and 0.073 g (0.000842 mol) of methacrylic acid. Air was introduced into the flask at 10 ml/min, and the reaction liquid was heated to 90° C. in an oil bath while stirring the reaction liquid. After the temperature of the reaction liquid reached 90°C, heating was continued for 3 hours so that the temperature of the reaction liquid became 89 to 91°C. Thereafter, the reaction liquid was cooled to room temperature, filtered, and the filtrate was subjected to GC analysis. The area percentage of chloroallyl methacrylate (CPMA) was 0.046%, the area percentage of glycidol was 0.756%, and the area percentage of 1,3-dichloro-2-propanol (DCP) was 0.035%. The area percentage of high boiling point impurities (the sum of diester, triester, and chlorohydrin propyl methacrylate) was 4.523%, and the area percentage of glycidyl methacrylate (GMA) was 93.6%.

Thereafter, the obtained reaction liquid was washed with water. Specifically, first, 8.8 g of a 0.57% by mass sodium hydroxide aqueous solution was mixed with the reaction liquid. The mixed solution was stirred at a stirring speed of 250 rpm for 15 minutes in a glass container equipped with a stirring blade, and the reaction solution was washed. Thereafter, the liquid was transferred to a separatory funnel, left still for 30 minutes, and separated into layers. Furthermore, the liquid which wash|cleaned the organic layer obtained by washing with water was distilled. Specifically, 21 g of the liquid for washing the organic layer was put into a flask, and single distillation was performed. After distilling off and recovering the remaining epichlorohydrin, the main fraction is distilled off at an internal temperature of 94-124°C, a tower top temperature of 71-85°C, and a pressure of 1.33-2.95kPa. Thus, 4 g of a distillate was obtained. The obtained distillation distillate was subjected to GC analysis. The area percentage of CPMA was 0.046%, that of glycidol was 0.076%, and that of DCP was 0.002%. The area percentage of high boiling point impurities was 0.000%, and the area percentage of GMA was 99.8%. In addition, by the measurement of the total chlorine content, it was confirmed that 214 ppm of impurities were contained in the distillate in the above-mentioned distillate in terms of the total chlorine content.

(Examples 2-13 and Comparative Examples 1-5)

Except for changing the type and amount of Bronsted acid added at the time of raw material addition in the reaction step to the values shown in Table 1, the reaction, water washing, and distillation were carried out in the same manner as in Example 1, and GC analysis and total chlorine content were performed. Determination. The results are shown in Table 1.

[Table 1]

This application claims priority based on Japanese Patent Application No. 2013-60041 filed on March 22, 2013, and Japanese Patent Application No. 2013-225341 filed on October 30, 2013, and the disclosures thereof are incorporated in this.

As mentioned above, although this invention was demonstrated with reference to embodiment and an Example, this invention is not limited to the said embodiment and an Example. In the configuration and details of the invention of the present application, various changes that can be understood by those skilled in the art can be made within the scope of the invention of the present application.

Industrial availability

Glycidyl (meth)acrylate produced by the method according to the present invention can be used for various paints, adhesives, adhesives, various reactive monomers, and the like.

Claims (5)

1. a kind of manufacture method of (methyl) glycidyl acrylate, is to make epoxychloropropane and (methyl) propylene acid alkali metal The method that salt reacts and manufactures (methyl) glycidyl acrylate in the presence of a catalyst, it includes：

In reaction system, relative to the Blang of 1 mole of (methyl) alkali metal salts of acrylic acids, 0.001 mole of presence~0.05 mole The process that Si Taide is sour and carries out the reaction.

2. the manufacture method of (methyl) glycidyl acrylate as claimed in claim 1, wherein, Bronsted acid is carboxylic At least one of acid and sulfonic acid.

3. the manufacture method of (methyl) glycidyl acrylate as claimed in claim 2, wherein, Bronsted acid is choosing From at least one of (methyl) acrylic acid, benzoic acid, acetic acid and methanesulfonic acid.

4. the manufacture method of (methyl) glycidyl acrylate as claimed in claim 1, it includes：

It will be washed by the obtained reaction solution that reacts, the liquid after washing stood and the work of organic washing layer is separated Sequence；With

By the process of the liquid distillation of organic washing layer.

5. such as the manufacture method of (methyl) glycidyl acrylate according to any one of claims 1 to 4, its feature exists In, in (methyl) glycidyl acrylate, the impurity containing below 500ppm in terms of total chlorine amount.